Lubricating oil



Patented Dec. 14, 1943 LUBRICATING OIL Eugene Lieber, Staten 'Island,- N. Y., -and Aloysius F. Cashman,-Bayonne, N. J., assignrs to Stand-l ard Oil Development Company, a corporation of Delaware Appueauon'oetober 4, i939, serial No, 297,987:r 1s claims..` ((1252-59) Y ''his invention relates to the production of lubricating oi1 compositions of low pour point and oi.' desirable color characteristics in both transmitted and reiiected light and to the compounds `incorporated therein which eilect such desirable features in lubricating compositions otherwise decient in these attributes.

The pour point, color and uorescent characteristics of an untreated petroleum distillate Vary while residuals tend tobe green; and acid treat-` ment tends to eliminate the green cast and cause-the development oi' a brownish-blue cast.:

The lubricating oil stocks from Pennsylvania crudes set the standard of color and cast inthe early days of the use of petroleum lubricants and today the green cast, or bloom. as it is com- .monly termed, of these oils is considered to be more advantageous, especially from the commercial sales viewpoint, than the blue or other cast appearance of lubricating oil stocks derived from the Coastalor highly naphthenic type crudes.V

In addition to the more pleasing appearance of these oils, a feature of utility of the green bloom" is that it conveys to the oil so characterized, a better visibility against a dark or light background than a blue or other color cast. The sales preference for lubricating oils possessed of low pour point, the acceptable olive or golden green cast 'and the reddishcolor by transmitted light, has established the need for the manufactureof lubricating oil addition agents which can suitably impart to composites these desired characteristics without adversely aiecting other desirable propertiesof the lubricating oil composition. The present invention relates to this eld.

An object therefore of the invention is the preparation-of a composition of matter which when admixed in small amounts imparts to lubricating oil stocks of poor cast and color characteristics, usually associated with oils derived .tion of lubricating oil compositions of low pour point and good color characteristics in both transmitted and reflected lights by incorporating -in-lubricating oil stocks deficient in these respects, small amounts of a compound the preparation of which is hereinafter disclosed.

In the preparation of thelubricating oil addition agent of this invention, according lto one method an organic compound of cyclic structure, such. as the aromatic hydrocarbons and their substitution' products, a low boiling alkyl polyhalide and a condensing agent are heated as a mixture to a pre-determined temperature and a low boiling alkyl mono-halide added, and heating continued for a suiilcient time to bring about the ,formation of a condensation product which separates when the reaction mixture is suitably hydrolyzed. A superior product is prepared by continuing the .condensation one step further. Thus, to the heated reaction mixture a small quantity of halogenated high molecular weight aliphatic compound, such as chlor-wax, is added and heating continued until a second condensal tion takes place.

' 'I'he cyclic hydrocarbon may be of aryl, alkaryl or heterocyclic structure, but preferably of condensed ring type such as an aromatic.f The aro` matic hydrocarbons which give superior products are benzene, naphthalene, anthracene and phenanthrene, and of these, naphthalene serves particularly Well. Derivatives of these .hydrocarbons such as halogeno (e. g., monochloro) hydroXy, alkoxy, amino, alkamino substitution products of aromatic hydrocarbons, which react similarly to thehydrocarbons themselves inl the condensation reaction, may also be employed. The low boiling alkyl polyhalides which have been found to be suitable are the dihalides of short chain aliphatic hydrocarbons, having less than l0 carbon atoms in the molecule but preferably containing from 1 to 5 carbon atoms and in which the chlorine atoms are in adjacent positions. Very suitable compounds of this class are dichlor-methane, dichlor-ethane and dibromo-propane. In. general', compounds which can be suitably employed instead 'of the low molecular Weight poly-halides, are any of the halo.

genated derivatives of the hydrocarbons containing up to six carbonatomsv and not more than' two halogen atoms per molecule. 'I'he llow boilingy aliphatic mono-halide may be any mono-halide derived from a lower saturated hydrocarbon such as propane, butane and pentane. Instead of the aliphatic halides, the corresponding olens may be used. Instead of the halogenated high molecular weight aliphatic compounds, the corresponding unsaturated derivatives may be used. Suitable condensing agents are those of the Friedel- Crafts type, namely aluminum chloride, zinc chloride, boron fluoride, and the like, but acid catalysts such as sulfuric and phosphoric acids, and known equivalents may also be used.

. As an illustration of this invention, the process is carried out by employing approximately equimolecular quantities of the cyclic hydrocarbon or the corresponding halogen derivative, and the low molecular weight aliphatic poly-halide, and about 20% of condensing agent with or without the use of an inert solvent, suchl as naphtha and inert highly chlorinated hydrocarbons such as tetrachlorethane, diand trichlor-benzol, etc. The mixture is mechanically stirred and heated to about 85 F. The aliphatic mono-halide is then gradually added to the mixture over a period of about 20 minutes while maintaining the reaction temperature at about 85 F. After the addition of the alkyl mono-halide, the reaction mixture is stirred at about 85 F. for ve hours in order to complete the initial part of the condensation. The temperature is then raised to the reflux point and maintained there for from 2 to 12 hours in order to complete the condensation. The product so obtained may be hydrolyzed by treating with a dilute hydrochloric acid solution, that is, a solution containing about hydrochloric acid.

Another method of preparing the dye material, and one which gives a product of improved cast and potency, is to treat the condensation product previously prepared with chlorinated para'in wax in an amount of 25% by Wei-ght of the reaction mixture by adding gradually over a 15 minute period while the temperature is held at about 230 F. The product so obtained may be hydrolyzed according to the details given for the rst process, or the reaction mixture may be diluted with ethylene dichloride, or some other suitable solvent, cooled to about 150 F., neutralized with an isopropyl alcohol-aqueous caustic solution, and after settling, the ethylene dichloride solution is distilled with re and steam to 600 F. to recover the dye product.

This method of preparing the lubricating oil addition agent bears some similarity to the process disclosed in the co-pending application of Eugene Lieber, Serial No. 245,673 now Patent No. 2,270,062. In that application, pour point depressants are prepared by the condensation of an alkylated cyclic compound with a di-halo organic compound. When the cyclic radical is of condensed structure such as in 'anthracena phenanthrene andv naphthalene, the condensation products obtained exhibited dye properties. The yields obtained in such cases are low and lthe preparation of dye products by that process is uneconomic.

In the present invention, the order of adding the reagents diiiers from that disclosed in the copending application, Serial No. 245,673 now Patent No. 2,270,062, and in the alternative method of preparing the dye product, the condensation is carried one step further than is disclosed in the co-pending application. The products obtained by the present process are more satis factorily soluble in all types of lubricating oil stocks, and the potency and the yields are considerably greater than those obtainable by the process disclosed in the co-pending application No. 245,673 now Patent No. 2,270,062.

The products prepared according to this invention are evaluated by standard tests for pour point and color characteristics of oil compositions. The pour` point of an oil is the temperature at which the oil fails to ow in the test jar under standard conditions. The potency of the dye product is estimated in terms of actual color units which are determined by dissolving the material in an oil of standard color, and evaluating the color change in the Robinson co1- orimeter. The determination of the cast or bloom imparting qualities depends largely upon the judgment or experience of the observer. The cast may be evaluated by means of a tint photometer and results expressed in the form of a color absorption graph, but this method is today very seldom employed. It is more usual to evaluate the cast by arranging a series of Pennsylvania oils and dyed pale oils in order of pleasing eiect on the e'ye, and rating the dyed oils with regard to the appearance of the Pennsylvania stocks.

The amount of the product employed for purposes of lowering the pour point and of dyeing lube oils decient in color and cast, depends greatly upon the extent of the deficiency and on the potency of the product. Usually, however, it is added to an oil in proportions varying from 0.5% to 4% of the oil, depending on the nature of the oil and the potency of the material. The preferable range is an amount varying from about 1% to 2% by volume of the oil.

The following examples will serve to illustrate the invention:

EXAMPLE 1 Into a 3-liter, 4-necked, round bottom ask, equipped with reflux condenser, dropping funnel. thermometer and provision for heating, was placed 280 grams of naphthalene, 220 grams of ethylene dichloride and 44 grams of aluminum chloride. The stirrer was started and the amyl chloride (mixed amyl chlorides of commerce) was added t0 the reaction mixture at such a rate that the reaction temperature did not exceed F. This required from 30 to 40 minutes. After the addition of the amyl chloride, the reaction mixture Was allowed to agitate for two hours at 90 F. and then the temperature was increased until the ethylene dichloride was vigorously refluxing (2l0-230 F.) and maintained thereat for two hours. The reaction mixture was diluted with ethylene dichloride (20D-400 cc.), cooled to F. and hydrolyzed with a mixture of alcohol and Water. After settling, the ethylene dichloride extract was distilled with fire and steam to 600 F. in order to remove the solvent and low boiling products. A bottoms residue comprising-306 grams (64% yield) of the dyecondensation product was obtained.

The distillate obtained up to 600 F. is settled and the water condensate removed'and discarded. The remainder is distilled to recover ethylene dichloride and about 15% of a low molecular weight condensation product. This low molecular weight condens ation product comprised chiefly di- (amyl -naphthyD -ethane HiiC-s- CH2CHF -CsHu and it was found that this material couid be converted to the same' valuable dye product by merely reluxing with ethylene dichloride in the presence of aluminum chloride, or that it may be recycled back to the process as described above.` The 64% yield previously given was calculated in this manner.

When 0.15% of this dye product was added to a petroleum distillate lubricating pale oil of 11 Robinson color, the blend had a 41/4 Robinson color and a brilliant red color by transmitted light and a pleasing green fluorescence. In addition a very good match of the glasson the colorimeter machine was obtained. To those skilled in the art, the signicance of thatv term is clear, i. e., the dyed pale oil approaches very closely to the appearance of a Pennsylvania oil in color and cast. The addition of 0.23% of the condensation product tothe same pale oil gave a blend of a 1% Robinson color with a much more intense brilliant red color and green bloom. On n the other hand, in order to obtain the same color the glass on the colorimeter machine and at the` same time it is deficient in green bloom, a fact 'able in the reflux of ethylene dichloride.

at which time a noticeable decrease was observ- 100 grams of chlorinated -parafn wax (121 F. M. P., chlorinated to 34.5 A. P. I. gravity was then added to the reaction mixture drop by drop over a period of minutes while maintaining a.' reaction temperature of 230-235 F. Reaction of the condensation-polymer with the chloro-wax was extremely vigorous under the conditions used which makes it unnecessary to prolong the reaction much beyond the total addition of the chloro-Wax. After the addition of all of the chloro-Wax, the reaction was continued for 15 minutes at 230-235 F., then diluted with 1000 which sets it aside immediately from the color l of Pennsylvania type oils.

EXAMPLE 2 The procedure and proportion of reagents of Example 1 was repeated exactly except that the time of reiiux or condensation period was increased from 2 to 4 hours. The dye-condensation product was recovered as previously described. A yield oi 66% was obtained. However, from the point of view of its use as a dye-stud,

the yield has practically doubled over Example l,

as subsequently indicated.

The dye-condensation products of Examples l and 2 and cracking coil tar dye were-'added to a pale oil of Robinson color 11 until 2 and 4 Robinson colors Were respectively obtained.

The following table shows the comparative results obtained:

Per cent Robinson Dye of dye color Match of glass None ll Cracking coil 1.00 2 Ol shade. Tar dye 0.50 4 Do. l From Example 1 35 vergt-god mmc l' From Example 2. 4 Do It will be observed that the dye product of Example 2 was twice as potent in tinctorial power as the dye product of Example 1. In comparison with cracking coil tar dye, the tinctorial power of the dye products of Examples 1 and 2 were from 2 to 4 times as powerful.

EXAMPLE 280 grams of naphthalene, 220 grams of ethyl- I ene dichloride and 44 grams of aluminum chlograms of ethylene dichloride and cooled to 125- l50 F. and neutralized with an isopropyl alcoholaqueous caustic solution. After settling, the ethylene dichloride extract was distilled with ire and steam to 600 F. to recover the dye product.

A total yield of 413 gramsof dry dye was obtained which corresponds to a 72.1 per cent yield based on all .of the reagents including the chloro-wax. Examination of the dyeing potency showed 7.8 105 actual color units.

EXAMPLE 4 The agitator comprised a 3-liter nickel yreaction vessel, similar in construction to the glass reactor described in Example l..

The following proportions of reagents were used:

Grams Naphth'alene i 280 Ethylene dichloride 220 Aluminum chloride' 44 Mixed amyl chlorides 236 Chlorinated wax (11.8% Cl) The procedure used for carrying out the dye synthesis was the same as described in Example 3. The dye-product was recovered as before by cooling the reaction mixture to about 10G-125 E., diluting with ethylene dichloride and decomposing the aluminum`chloride with an isopropyl alcohol-aqueous caustic solution. After settling, the ethylene dichloride extract is distilled with fire and steam to 600 F. to recover the dye product.

A total yield of 361 grams of dry dye was obtained which vcorresponds to a 63.1% yield based on all of the reagents including the chloro-wax. Examination of the dyeing potency showed 6.1 X actual color units.

The dye prepared as described above Jas added to various oils, whose original inspections are indicated in the table given below', for color deepening and cast improvement.

The following table summarizes the results obtained:

Oil #2 Mg. dry dye/100 ml. oil 0 Inspections Flash "F Viscosity 100 F Viscosity 210 F Viscosity index Robinson color Color hold (16 hrs. 210 F.) Daylight stability (10 days). Conrarison carbon Ramsbottom coke A Ramsbottom coke B Sligh oxidation test Oxygen absorption testhours (r 48 hours 72 hours It will be observed from an inspection of the table that the dye had no deteriorating eiect upon the quality of the oil.

Attention is directed to the stability of the dye tilled with fire and steam to 600 F., in order to remove the solvent and to recover the dry dye.

A total yield of 58 grams of dry dye was obtained. This corresponds to a 22% yield based product under severe conditions of test. Samples on all reagents. A determination of the dyeing of dyed oils '#1- and #2 containing 100 mg. of the dry dye (see table) were placed in a thermostaticallycontrolled oven at 210 F. for 16 hours. It Will be observed from the table that the dyed samples underwent practically no change, while The following example illustrates the use of the lower olefins in place of the low boiling aliphatic mono-halides.

The following reagents were used in the proability showed 2.8 105 actual color units. Further, the green cast. imparted to the oil is of an inferior quality compared to the dye made by the present process.

EXAMPLE 8 The following is a comparison of the cast or bloom of dyed pale oils (viscosity of 200 Saybolt Universal seconds at 100 F.) and correspondingly representative Pennsylvania oils.

Procedure The following samples matched to give 2 Robinson color were placed in 4'oz. bottles and comtion and for recovery of product was the same as described for Example 3.

A total yield of 72 grams of dry dye was obtained which corresponds to a 58% yield based on all the reagents.. Examination of the dyeing potency showed 5.8 105 actual color units. The dyed oils showed a good cast and an excellent through red color.

When 2% of the dry dye, obtained as described l above, was added to a waxyoil,the.pour point of which was F., the pour point was found to be 10 F.

` EXAMPLE 6 The following example illustrates the pour depressant potency of the products of this invention.

The dye product tested'was that obtained in Example 3. This was blended in various conceny' EXAMPLE 7 The following example is oifered as a. distinction of the present invention from the process outlined in co-pending application Serial No. 245,673. f

The following reagents:

. Grams Mono-amyl naphthalene 200 Ethylene dichlorlde 220 Aluminum chloride 22 were reacted by the procedure of co-pending application Serial No. 245,673, now Patent No. 2,270,062, i. e., by heating to the reflux temperature of the ethylene dichlorlde and maintaining thereat for 3 hours, at which time the reaction mixture was cooled, diluted with ethylene dichloride and thealuminum chloride decomposed by the addition of alcohol'and water. The ethylene dichlorlde extract, after settling, was dis- 1 to 3 iiltered Penn. Bright stocks 5 pale oil-l-dye product of Exp. 1.....

S'Pale oil-l-Com. cracking coiltar dye.

0 through the same opening.

The oils were examined and placed in order of'cast from golden green to bluish green.

' Order of cast Remarks Goldengreen bloom showing little distinction.

Golden green bloom slightly less marked than above.

Golden green bloom but green more pronounced.

Grass green with no pronounced golden color.

4 pale-oil-l-dye product of Exp. 3.....

6 to 7 unfiltered Penn. Bright stocks.

EXAMPLE 9 ,In effecting the invention upon a semi-plant scale, .equi-molecular proportions of naphthaiene, ethylene dichlorlde and mixed amyl chlorides .were used'together with 20% by weight anhydrous aluminum chloride based on the ethylene dichlorlde and. 90% by weight'of chlor-wax (12% Cl) based on the ethylene dichlorlde. 'I'he apparatus 4employed is dlagrammatically represented in the accompanying drawing to which relate the numerals used in the following description.

Naphthalene (138 lbs.) was added through a removable cap 8 to' a nickel'lined reactor 1, connected by vapor line 9 to a condenser` I0 fitted with gas outlet I2 through look box II. v Ethylene dichlorlde (110 lbs.) was pouredl in ,Aluminum chloride (20 lbs.) was added through this opening and then the cap was replaced and the mixer started. Mixed amyl chlorides (1201/2 lbs.) were then placed in the blowcase'1 2 through the re movable cap I in the top. The case was sealed chloride blown through look box 5 into the reactor over a. period of 1% hours. Valves 3 and 4 were closed and valve I3 opened. Temperature of the reactor was maintained at F.

1The blowcase 2 could be replaced with a gravity feed 75 tank for the addition of liquids to the reactor.

'of steam stripping done.

Agitation was continued for 2 hours, the temperature of the reactor being maintained at 80 F. Chlor-wax (12% Cl) (100 lbs.) was then placed in the blowcase and was blown over into the reactor over a period of 2 hours, the temp erature of the reactor being maintained at 90 for 16 hours, vigorous agitation being main- A tained throughout. It was then heated by means i of, a steam coil to 185 F. over a period of ve hours. At 185 F. refiuxing started. The temperature was then allowed to rise naturally as the refluxing permitted. Maximum temperature was 226 F. The reiiuxing was continued for 'l hours, then the reactor was cooled, diluted with 30 gallons of ethylene dichloride, and neutralized by blowing into the reactor through the blowcase 45 gallons of water, 10 gallons of 38 Baume caustic soda, and 8 gallons of 91% isopropyl alcohol. Agitation was then Stopped and the mixture allowed to settle overnight. The sludge. was then separated by opening valves I4 and l5. The valves were closed and then 20 gallons of kerosene and 20 gallons (153 lbs.) of very heavy cable oil were added to the contents of reactor 1.' This mixture was charged to the still l1 by opening valves Ill and i6. A

The still was fired and the ethylene dichloride, kerosene, and unreacted low boiling materials taken overhead by a fire and steam distillation to 600 F., and cooled in condenser I8. The residue after cooling was removed through valve I9. This residue was a very viscous oil and weighed 313 lbs.

subtracting the 153 lbs. of cable oil which does not distill under these conditions, there was in the still bottoms, 160 lbs. of dye concentrate. This corresponds to a per cent weight yield of 48.5%.

The following inspections were made on the still bottoms:

S. U. viscosity 210 F seconds 199 A. P. I. gravity (D 60 F degrees-- 16.7 O. C. ash point 465 O. C. re point.V F 525 Cl per cent-- 0.18 Dye value a. c. u.-- 264x105 Neut. No 0.05 Saponication No 0.60

A small portion of the ethylene dichloride solution was reduced separatelywith no cable oil in the still. The concentrate is a dark brown resin which can be powdered. It is soluble in all proportions in petroleum lubricating oils. The melting point of the resin varies with the amount The powdered material is dark brownish red in color.

It is to be understood that the scope of the invention is not to be limited by or to the examples given, which are presented merely for the purpose of illustration and that modications and variations may be made therein without departing substantially from the spirit of the invention.

We claim:

1.` A condensation product soluble in lubricating oil and having the properties of depressing the pour point of waxy lubricating oils, and of imparting to lubricating oils of poor color and cast characteristics a deep reddish color by transmitted light and a golden green color by reected light, comprising a condensation product prepared by adding a low boiling aliphatic compound containing not substantially more than 5 carbon F. The reactor was then maintained at 85 F.

atoms of the class consisting of saturated monohalides and the corresponding unsaturated compounds to an unreacted mixture of an aromatic compound and an aliphatic poly-halide having less than 10 carbon atoms and rot more than 2 halogen atoms and a condensing agent and heating to a. reaction temperature.

2. A condensation product soluble in lubricating oil and having the properties of depressing the pour point of waxy lubricating oils and of imparting to lubricating oils of poor/ color and cast characteristics a deep reddish color by transmitted light and a golden green color by reiiected light, comprising a condensation product prepared by adding a low boiling alkyl monohalide containing not more than 5 carbon atoms to an unreacted mixture of an aromatic hydrocarbon, an aliphatic poly-halide having less than 10 carbon atoms and not more than 2 halogen atoms and a condensing agent and heating to a reaction temperature.

3. A condensation product soluble in lubricating oil having the properties of depressing the pour point of waxy lubricating oils and of imparting to lubricating oils of poor color and cast characteristics a deep reddish color by transmitted light and a golden green color by reflected light, vcomprising a condensation product prepared by adding amyl chloride to'an unreacted mixture of naphthalene and ethylene dichloride and a condensation agent of the Friedel-Crafts type and heating to a reaction temperature.

4. An improved condensation product soluble in lubricating oil and having the properties of depressing the pour point or waxylubricating oils and of imparting tolubricating oils deflcent in color and cast characteristics a deep reddish color by transmitted light and a golden green color by reilected light, comprising a condensation product preparen-l by the reaction of an aromatic compound and an aliphatic di-halide having less than 10 carbon atoms with a low boiling aliphatic compound containing not substantially more than 5 carbon atms of the. class consisting of saturatless than 6 carbon atoms, an alkyl mono-halide having 3 to 5 carbon atoms and a condensing agent of the Friedel-Crafts type, and the subsequent condensation of said product with a halogenated high molecular weight aliphatic compound.

6. An improved condensation product soluble in lubricating oils and having the properties' of depressing the pour point of waxy lubricating oils and of imparting to lubricating oils deicient in color and cast characteristics a deep reddish color by transmitted light and a-golden green color by reiiected light, comprising a condensation product of the reactions of naphthalene, ethylene dichloride, amyl chloride and aluminum chloride at a temperature between about 85 F. and reux temperature, and the subsequent condensation of light and a golden green color by reected light,

comprising adding a low boiling aliphatic compound containing nct substantially more than carbon atoms of the class consisting of saturated monolhalide and the corresponding unsaturated compounds to an unreacted mixture of an aromatic compound and an aliphatic poly-halide having less than 10 carbon atoms and not more than 2 halogen atoms and a condensing agent and heating to a reaction temperature.

8. An improved process for preparing lubricating oil addition agents having the properties of being soluble in lubricating oils of depressing the pour point of waxy lubricating oils and of imparting to lubricating oils deficient in color and cast characteristics a deep reddish color by transmitted light and a golden green color by reflected light, comprising adding a low boiling aliphatic compound having 3 to 5 carbon atoms of the class consisting of saturated mono-halides and light, comprising a lubricating oil of undesirable color characteristics and a small amount, effective. in improving the color characteristics of said oil, of the product described in claim l.

13. An improved lubricating oil having the desirable characteristics of deep red color by transmitted light and a golden green color by reflected light comprising a lubricating oil of undesirable color characteristics and a small amount, effective in improving the color characteristics of said o-il, of the product described in claim 4.

14. An improved lubricating oil having the desirable characteristics of deep red color by transmitted light and a. golden green color by reflected vlight comprising a lubricatingoil of ,undesirable color characteristicsand a small amount, effective in improving the color characteristics of said oil, of the product described in claim 6.

15. Animproved process for preparing lubrieating oil` addition agents having the properties of being solublein lubricating oils and cf impartthe corresponding unsaturated compounds to an l unreacted mixture of an aromatic hydrocarbon compound, an aliphatic di-#halide having less than 6 carbon atoms and a Friedel-Crafts condensing agent, heating the mixture to a reaction temperature, and subsequently condensing product of said reaction with a halogenated high molecular weight aliphatic compound.

9. An improved lubricating oil of low pour point and of deep red color by transmitted light and a golden green color by reflected light, comprising a lubricating oil and a product of claim 1.

10. An improved lubricating oil of low pour point and of deep reddish color by transmitted light and a golden green color by reflected light,

comprising a lubricating oil and a product of claim 4.

11. An improved lubricating oil of low pour point comprising a waxy lubricating oil having normally a high pour point and a small amount, eiective in reducing the pour point of said oil, of the product described in claim 1.

12. An improved lubricating oil having desirable characteristics of deep red color` by transmitted light and golden green color by reflected ing to lubricating oils deficient in color and cast characteristics a deep reddish color by transmitted light and a golden green colorrby reected light comprising adding a low boiling aliphatic compound having 3 to 5carbon' atoms of the class consisting of saturated monohalides and the corresponding unsaturated compounds to an unreacted vmixture of naphthalene, an aliphatic dichloride having less than 6 carbon atoms and a Friedel-Crafts condensing agent, heating the mixture to a reaction temperature between the approximate limits of F. and reux temperature, and subsequently condensing the product o f said reaction with a halogenated high molecular weight aliphatic compound.

16. The process which comprises mixing approximately equirnolecular quantities of naphthalene and ethylene dichloride, adding about 20% by weight of aluminum chloride, based on the weight of ethylene dichloride used, stirring and heating the mixture to about 85 E. Without causing any substantial reaction, gradually adding thereto an approximately equimolecul'ar amount of mixed amyl chloride, maintaining the resultant mixture at about 85 F. to complete the initial part of the condensation, then raising the temperature to reflux temperature and maintaining it thereat for about 2 to 12 hours to complete the condensation, and hydrolyzing and removing the catalyst. I

EUGENE LIEBER. ALOYSlUS F. CASHMAN. 

